WO2018174626A2 - Acid-resistant nano-separation membrane having enhanced flow rate, and method for manufacturing same - Google Patents

Abstract

The present invention relates to an acid-resistant nano-separation membrane having an enhanced flow rate, and a method for manufacturing same, and more particularly, to an acid-resistant nano-separation membrane having an enhanced flow rate, wherein the nano-separation membrane can be used in strongly acidic and high-temperature conditions to recover rare metals and precious metals and the like that are generated during a smelting process, and exhibits the effect of having both an excellent flow rate and excellent acid resistance, and a method for manufacturing the same.

Description

Acid resistance nanomembrane with improved flow rate and manufacturing method thereof

The present invention relates to an acid resistant nano-separation membrane with improved flow rate and a method for manufacturing the same, and more particularly, to recover rare metals and valuable metals generated in a smelting process, and can be used under strong acid and high heat conditions, and have excellent flow rate and acid resistance. The present invention relates to an acid resistant nano separator and a method for manufacturing the same having improved flow rates.

Metal-containing wastewater includes mine wastewater, chemical plant wastewater, smelter wastewater, steel mill wastewater, plating plant wastewater and garbage incinerator wastewater. Among these, the electroplating plant wastewater generated from the steel mill has a low pH of 2-4, and contains complex metal ions such as nickel, zinc, tin, chromium, and copper in addition to iron ions (divalent) depending on the plating type. There are many cases. These metal ions are hazardous metals and are subject to wastewater regulations and must be removed below legal limits before discharge. However, if it can be separated and recovered as a metal, it can create value as a resource. In addition, the plating plant wastewater may contain organic substances such as surfactants and plating additives, and may require additional COD (chemical oxygen demand) treatment.

Hereinafter, the treatment method of the conventional plating wastewater is demonstrated.

A typical treatment method of plating wastewater widely used in the past is a neutralized flocculation precipitation method. In this method, an inexpensive alkaline agent such as calcium hydroxide is administered to raise the pH of the wastewater to 9 to 10, and the metal ions contained in the wastewater are hydroxideized to precipitate and separate into a sedimentation basin. At pH 9-9, iron ions, nickel ions, zinc ions, etc., are hydrated with reduced solubility. However, the pH-adjusted precipitation method generates chemical sludge containing various metal ions, and the sludge is treated by landfilling as defined by law because it is not reused and is classified as special waste.

In addition, sulfide precipitation, ion exchange resin, chelate resin membrane separation, solvent extraction, bioconcentration, activated carbon adsorption, and the like are treated as electroplating wastewater.

Among them, the membrane method transfers only the solvent through the membrane using the permeation pressure, so that clean and clean treated water can be obtained, which is widely used for desalination of seawater and reuse of plant wastewater. However, a high concentration of salts will occur at the same time. It also requires cumbersome cleaning or pretreatment of the membrane and high pressure. Due to the principle of the membrane method, selective separation and concentration of specific metal ions is not possible.

In addition, the membrane method is sometimes applied to reuse of plating wastewater. In this case, not only heavy metals but also inorganic ions can be removed from raw water, so that the membrane permeated water can be reused as industrial water. At the same time, however, a small amount of concentrate is produced, and it contains various heavy metal ions and inorganic ions, which makes it difficult to reuse, and the maintenance costs are high due to poor use conditions such as high temperature, high pressure and strong acid conditions.

Therefore, there is a need to develop an acid resistant separator that can be used under strong acid and high temperature conditions to recover rare metals and valuable metals from the wastewater.

Meanwhile, in the related art, a sulfonyl halide was introduced into an aqueous amine solution to form a sulfone amide layer, thereby preparing a nano separator having acid resistance. It can be applied to the process of generating acid wastewater such as smelting industry that needs acid resistance, but it can be used in strong acid and high temperature condition to recover rare metals and valuable metals generated in smelting process, and it has excellent flow rate and excellent acid resistance. There was a problem that was difficult to show the effect.

The present invention has been made to solve the above problems, the problem to be solved of the present invention can be used in strong acid and high temperature conditions to recover the rare metals and valuable metals generated in the smelting process, and the flow rate is excellent It is to provide an acid resistant nano-separation membrane and a method for producing the same having an improved flow rate showing the excellent acid resistance.

In order to solve the above problems, the present invention comprises the steps of immersing a porous support in a first solution comprising a first amine compound, a second amine compound and a phenol compound comprising a compound represented by the formula (1); Treating the immersed porous support with a second solution including an acid halogen compound to form a polyamide layer on the surface of the porous support; And hydrophilizing the porous support on which the polyamide layer is formed.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₁₀ alkylene group, and n is an integer of 1 to 100.

According to a preferred embodiment of the present invention, in Formula 1 R ¹ and R ² may be each independently C ₂ ~ C ₆ linear alkylene group or C ₂ ~ C _{6 It} may be a crushed alkylene group, n May be an integer from 1 to 10.

According to another preferred embodiment of the present invention, the phenolic compound may include one or more selected from the group consisting of pyrocatechol, resorcinol, hydroquinone, pyrogallol and phloroglucinol.

According to another preferred embodiment of the present invention, the second amine-based compound may include one or more selected from the group consisting of metaphenylenediamine and piperazine.

According to another preferred embodiment of the present invention, the first solution may include a first amine compound, a second amine compound and a phenol compound in a weight ratio of 1: 0.04 to 2: 0.02 to 1.

According to another preferred embodiment of the present invention, the first solution comprises one or more selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol with respect to 100 parts by weight of the first amine compound The hydrophilic polymer may be included in an amount of 0.4 to 40 parts by weight.

According to another preferred embodiment of the present invention, the acid halogen compound may include one or more selected from isophthaloyl chloride, trimesoyl chloride and terephthaloyl chloride.

According to another preferred embodiment of the present invention, the hydrophilization treatment may be performed through a hydrophilization solution of 0.01 ~ 2% concentration.

According to another preferred embodiment of the present invention, the hydrophilization solution may include one or more selected from the group consisting of potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydroxide, sulfuric acid, sodium sulfate, sodium sulfite and sodium hydrogencarbonate Can be.

According to another preferred embodiment of the present invention, the hydrophilization treatment may be performed for 10 minutes to 90 ℃ for 0.1 to 5 minutes.

According to another preferred embodiment of the present invention, the porous support may include a nonwoven fabric and a porous polymer layer, the porous polymer layer may have an average thickness of 10 ~ 200㎛, polysulfone, polyethersulfone, It may be formed including one or more selected from the group consisting of polyimide, polypropylene and polyvinylidene fluoride.

On the other hand the present invention to solve the above problems the porous support; And a first solution including a first amine compound, a second amine compound, and a phenolic compound including a compound represented by the following Chemical Formula 1 on the surface of the porous support, and a second solution including an acid halogen compound. And a polyamide layer formed by interfacial polymerization, wherein the polyamide layer provides an acid resistant nanoseparation membrane having an improved flow rate with hydrophilic surface modification.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₁₀ alkylene group, and n is an integer of 1 to 100.

According to a preferred embodiment of the present invention, the polyamide layer may have an average thickness of 0.05 ~ 1 ㎛, the porous support is a non-woven fabric having an average thickness of 30 ~ 300 ㎛ and a porous polymer having an average thickness of 10 ~ 200 ㎛ It may include a layer, the porous polymer layer may be formed including one or more selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride.

According to another preferred embodiment of the present invention, the nano separator may have a flow rate of 25 gfd or more at 25 ° C. and 75 psi, and may have a salt removal rate of 90% or more.

According to another preferred embodiment of the present invention, the nano-membrane membrane may be 30 gfd or more at 25 and 75 psi when immersed in 15 wt% sulfuric acid aqueous solution for 30 days, the salt removal rate may be 85% or more.

On the other hand, in order to solve the above problems, the present invention provides a membrane module including the above-described nano-membrane membrane.

The acid resistant nano-membrane having an improved flow rate of the present invention and a method of manufacturing the same can be used under strong acid and high heat conditions to recover rare metals and valuable metals generated in the smelting process, and have excellent flow rate and excellent acid resistance.

Hereinafter, the present invention will be described in more detail.

As described above, in the past, sulfonyl halides were introduced into an aqueous amine solution to form a sulfone amide layer, thereby preparing a nano separator having acid resistance. It can be applied to the process of generating acid wastewater such as smelting industry that needs acid resistance, but it can be used in strong acid and high temperature condition to recover rare metals and valuable metals generated in smelting process, and it has excellent flow rate and excellent acid resistance. There was a problem that was difficult to show the effect.

Accordingly, the present invention comprises the steps of immersing the porous support in a first solution containing a specific compound; Treating the immersed porous support with a second solution including an acid halogen compound to form a polyamide layer on the surface of the porous support; And hydrophilizing the porous support on which the polyamide layer is formed. The above-described problem was sought by providing a method for producing an acid resistant nanomembrane having an improved flow rate.

Through this, it can be used under strong acid and high heat conditions to recover the rare metals and valuable metals generated in the smelting process, and can achieve the effect of excellent flow rate and excellent acid resistance.

First, the step of immersing the porous support in the first solution containing a specific compound will be described.

In the step of immersing the first solution, the polyamide layer may be formed on the surface of the porous support by treating the second solution containing an acid halogenide compound in a subsequent step by immersing the porous support in the first solution.

In general, the polyamide nanoseparation membrane may form a membrane by interfacial polymerization using a material that reacts with the polyfunctional amine, and the polyfunctional amine is a polyamine having 2-3 amine functional groups per monomer and is a primary amine or secondary Amines.

The first solution includes a first amine compound, a second amine compound, and a phenol compound.

The first amine compound includes a first amine compound including a compound represented by the following Formula 1 to improve salt removal rate and acid resistance.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently C ₁ ~ C ₁₀ Alkylene group, n is an integer of 1 to 100, preferably R ¹ and R ² are each independently C ₂ ~ C ₆ It may be a straight chain alkylene group of or C ₂ ~ C _{6 It} may be a branched alkylene group, n may be an integer of 1 to 10.

In addition, the second amine-based compound may be used without limitation as long as it is a material capable of improving salt removal rate in the art, and preferably includes one or more selected from the group consisting of metaphenylenediamine and piperazine. And more preferably using piperazine is advantageous for improving the salt removal rate.

In addition, the phenolic compound may be used without limitation as long as it is a substance capable of improving flow rate in the art, and preferably, the group consisting of pyrocatechol, resorcinol, hydroquinone, pyrogallol and phloroglucinol. It may include at least one selected from, more preferably may comprise at least one selected from the group consisting of pyrocatechol, resorcinol and hydroquinone, more preferably using resorcinol It is advantageous to significantly improve the flow rate. By including the phenolic compound, it is possible to improve the flow rate by hydrophilic modification of the surface of the polyamide layer to be formed later.

On the other hand, the first solution is a weight ratio of the first amine compound, the second amine compound and the phenol compound in a weight ratio of 1: 0.04 ~ 2: 0.02 ~ 1, preferably 1: 0.06 ~ 1.6: 0.04 ~ 0.8 It can be included as.

If the weight ratio of the first amine-based compound and the second amine-based compound is less than 1: 0.04, the salt removal rate may be significantly lowered. If the weight ratio is greater than 1: 2, a problem may occur in that the flow rate is not good. In addition, if the weight ratio of the first amine compound and the phenolic compound is less than 1: 0.02, the effect of improving the flow rate may be insignificant, and if the weight ratio is greater than 1: 1, problems of salt removal rate and acid resistance may be significantly reduced. have.

On the other hand, the first solution may include a hydrophilic polymer.

The hydrophilic polymer may be used without limitation as long as it is a hydrophilic polymer commonly used in the art, preferably may include one or more selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol, More preferably, polyvinylpyrrolidone can be used.

The first solution may include 0.4 to 40 parts by weight of hydrophilic polymer, preferably 1 to 35 parts by weight, based on 100 parts by weight of the first amine compound. If the hydrophilic polymer is included in an amount less than 0.4 part by weight based on 100 parts by weight of the first amine compound, a problem may occur that the initial flow rate and acid resistance are not good. If the content exceeds 40 parts by weight, the salt removal rate and the acid resistance are not good. May occur.

Meanwhile, the porous support may include a nonwoven fabric and a porous polymer layer.

The nonwoven fabric can be used without limitation as long as it is a nonwoven fabric of the specification commonly used in the art, preferably an average thickness of 30 ~ 300㎛, more preferably an average thickness of 50 ~ 200㎛, but is not limited thereto. Do not.

In addition, the porous polymer layer may be a porous polymer layer formed of a material that can be commonly used, preferably one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride It may be formed to include the above, the average thickness may be 10 ~ 200㎛, preferably 30 ~ 190㎛ average thickness, but is not limited thereto.

Next, the step of forming a polyamide layer on the surface of the porous support by treating the immersed porous support with a second solution containing an acid halide compound.

In the step of forming the polyamide layer, the porous support is immersed in the first solution in the immersion step described above, and the polyamide layer is made by reacting a first solution remaining on the surface with a second solution containing an acid halide compound. Can be formed.

The acid halogen compound may be used without limitation as long as it is a material capable of forming a polyamide layer. Preferably, the acid halogen compound may be at least one selected from isophthaloyl chloride, trimesoyl chloride and terephthaloyl chloride, and more preferably. Preferably trimezoyl chloride can be used. When trimesoyl chloride is used as the acid halogen compound, excellent salt removal rate can be exhibited.

In addition, the second solution may contain 0.005 to 2% by weight, preferably 0.01 to 1% by weight, of the acid halogen compound, based on the total weight of the second solution. If the acid halogen compound is less than 0.005% by weight, a problem that a polyamide layer is difficult to form may occur. If the acid halogen compound is more than 2% by weight, the acid halogen compound may be precipitated, thereby making it difficult to interface-polymerize easily.

Forming the polyamide layer may include a step of drying. The drying is not limited as long as the general drying conditions, preferably may be dried for 10 minutes to 10 minutes at 10 ℃ to 100 ℃, more preferably 1 to 10 minutes at 15 ℃ to 90 ℃.

On the other hand, the polyamide layer formed may have an average thickness of 0.05 ~ 1㎛, preferably 0.1 ~ 900㎛, but is not limited thereto.

Next, a step of hydrophilizing the porous support on which the polyamide layer is formed will be described. By performing the hydrophilization treatment, the surface of the polyamide layer may be hydrophilized to further improve the flow rate.

The hydrophilization solution is not particularly limited as long as it is a material capable of hydrophilic modification of the surface of the polyamide layer, preferably can be carried out through a hydrophilization solution containing an acid or a base material, more preferably hydroxide Potassium, calcium hydroxide, magnesium hydroxide, sodium hydroxide, sulfuric acid, sodium sulfate, sodium sulfite and sodium hydrogen carbonate can be carried out through a hydrophilic solution containing at least one selected from the group consisting of sodium hydroxide most preferably Performing through a hydrophilic solution is advantageous to significantly improve the flow rate.

In addition, the hydrophilization treatment may be performed through a hydrophilization solution having a concentration of 0.01 to 2%, preferably through a hydrophilization solution having a concentration of 0.015 to 1.8%. If the concentration of the hydrophilization solution is less than 0.01%, the effect of improving the flow rate may be insignificant, and if it exceeds 2%, a problem may occur in that the removal rate is lowered as the polyamide layer is decomposed.

The hydrophilization treatment may be performed by immersing the porous support on which the polyamide layer is formed in a hydrophilization solution. The hydrophilization treatment may be performed at 10 to 90 ℃ for 0.1 to 5 minutes, preferably at 15 to 80 for 0.2 to 3 minutes. If the hydrophilization treatment temperature is less than 10, the effect of improving the flow rate may be insignificant, and if the temperature exceeds 90, the problem may occur that the removal rate is lowered. In addition, if the hydrophilization treatment time is less than 0.1 minutes, the effect of improving the flow rate may be insignificant, and if it exceeds 5 minutes, the removal rate may decrease as the polyamide layer is decomposed.

On the other hand, after performing the above-described hydrophilization treatment, the unsupported residue may be removed by immersing the porous support subjected to the hydrophilization treatment in a buffer solution. More specifically, the porous support is immersed in a buffer solution for 0.5 to 24 hours at a water temperature of 10 ℃ ~ 95 ℃, preferably 1 to 5 hours at a water temperature of 15 ℃ ~ 90 ℃ and washed with distilled water The reaction residue can be removed.

The buffer solution may be used without limitation as long as it is a material capable of serving as a buffer solution, and may preferably include sodium carbonate. In addition, the buffer solution may include 0.05 to 0.5% by weight of sodium carbonate, preferably 0.1 to 0.4% by weight based on the total weight of the buffer solution, but is not limited thereto.

On the other hand, the nano-membrane prepared through the above-described manufacturing method has a flow rate of 25 gfd or more at 25 ℃ and 75 psi, the salt removal rate may be 90% or more, 25 ℃ and 75 when immersed in 15 wt% sulfuric acid aqueous solution for 30 days At psi, the flow rate may be at least 30 gfd and the salt removal rate may be at least 85%.

Hereinafter, the present invention will be described through the following examples. At this time, the following examples are only presented to illustrate the invention, the scope of the present invention is not limited by the following examples.

[ Example ]

Example  1: Preparation of nano separator

1 wt% of a compound represented by the following formula (1) using a porous polysulfone support having a thickness of 140 μm cast on a nonwoven fabric having an average thickness of 100 μm as a first solution, 0.35 wt% of resorcinol as a phenolic compound, and a second amine compound After immersing in an aqueous solution containing 0.5% by weight of low piperazine and 0.05% by weight of polyvinylpyrrolidone with a hydrophilic polymer for 40 seconds, the support on which the first solution was applied to the surface was treated with an acid halide compound as a second solution. It was immersed in an organic solution containing 0.02% by weight of monochloride for 1 minute to perform interfacial polymerization. Thereafter, the mixture was dried at 25 ° C. for 1.5 minutes to form a polyamide layer on the surface, and then immersed in an aqueous solution containing sodium hydroxide at a concentration of 0.15% for 1 minute with a hydrophilic solution, followed by hydrophilization. Was immersed in a buffer solution containing 0.2% by weight for 2 hours to remove the acid or unreacted residues to prepare an acid resistant nano separator.

[Formula 1]

In Formula 1, R ¹ and R ² are each an ethylene group, and n is 2.

Example  2 to 24 and Comparative example  1 to 8

In the same manner as in Example 1, the content of the first amine-based compound, the second amine-based compound and the phenolic compound, the type of the compound represented by the formula (1), hydrophilic solution as shown in Table 1 to Table 6 And nano hydromembrane was prepared by changing the presence or absence of hydrophilization treatment.

Experimental Example  1: flow rate, Salt removal rate  And Desalination  Rate of change

In order to evaluate the performance of the nano-membrane membrane, the permeate flow rate of the nano-membrane prepared according to Examples 1 to 24 and Comparative Examples 1 to 8 was measured at 25 and 75 psi in a 2000 ppm sodium chloride solution, and 2000 ppm magnesium sulfate The salt removal rate was measured under conditions of 25 and 75 psi in aqueous solution. After immersing in 15 wt% sulfuric acid solution for 30 days and then the permeate flux and salt removal rate were measured in the same manner. In addition, the rate of change of the salt removal rate was measured by the same method as in Equation 1 below. This is shown in Tables 1 to 6 below.

[Equation 1]

% Change in salt removal rate =% salt removal after 30 days immersion-initial salt removal rate (%)

Experimental Example  2 : Contact angle  And Contact angle  Change assessment

In order to evaluate the performance of the nano-membrane, the nano-membrane prepared according to Examples 1 to 24 and Comparative Examples 1 to 8 were measured using a contact angle measuring device (DSA 100, KRUSS). Distilled water was used for the contact angle measurement. Thereafter, the contact angle was measured in the same manner after immersion in 15 wt% sulfuric acid solution for 30 days. In addition, the rate of change of the contact angle was measured by the same method as in Equation 2 below. This is shown in Tables 1 to 6 below.

 [Equation 2]

Change in contact angle (°) = contact angle (°) after 30 days immersion-initial contact angle (°)

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 First solution Formula 1 (n = 2, wt%) One One One 0.6 0.6 One Formula 2 (n = 3, wt%) - - - - - - Second Amine Compound (wt%) 0.5 0.02 0.1 One 1.5 0.5 Phenolic Compounds (wt%) 0.35 0.35 0.35 0.35 0.35 0.01 First and Second Amine Compound Weight Ratio 1: 0.5 1: 0.02 1: 0.1 1: 1.67 1: 2.5 1: 0.5 First Amine and Phenolic Compound Weight Ratio 1: 0.35 1: 0.35 1: 0.35 1: 0.58 1: 0.58 1: 0.01 Second solution H ₂ SO ₄ (% concentration) - - - - - - NaOH (% concentration) 0.15 0.15 0.15 0.15 0.15 0.15 Early Flow rate (gfd) 32.7 34.3 28.2 26.6 21 23.1 Salt removal rate (%) 98.4 88.6 91.7 98.9 99.1 98.7 Contact angle (°) 39 38 41 40 43 45 30 days later Flow rate (gfd) 39.7 40.3 38.3 39.2 24.9 27.3 Salt removal rate (%) 95.1 82.5 94.3 95.3 89.2 96.3 Contact angle (°) 35 30 34 34 38 39 Salt removal rate change rate (%) -3.3 -6.1 -3.4 -3.6 -9.9 -2.4 Contact angle change (°) -4 -8 -7 -6 -5 -6

division Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 First solution Formula 1 (n = 2, wt%) One 0.55 0.62 0.3 0.5 2.5 Formula 2 (n = 3, wt%) - - - - - - Second amine compound (% by weight) 0.5 0.5 0.5 One 0.5 0.5 Phenolic Compounds (wt%) 0.05 0.5 0.8 0.35 0.35 0.35 First and Second Amine Compound Weight Ratio 1: 0.5 1: 0.9 1: 0.8 1: 3.3 1: 1 1: 0.2 First Amine and Phenolic Compound Weight Ratio 1: 0.05 1: 0.9 1: 1.3 1: 1.17 1: 0.7 1: 0.14 Second solution H ₂ SO ₄ (% concentration) - - - - - - NaOH (% concentration) 0.15 0.15 0.15 0.15 0.15 0.15 Early Flow rate (gfd) 25.3 39.4 44.7 28.4 27.2 26.5 Salt removal rate (%) 99 90.1 77.6 89.2 98.1 98.6 Contact angle (°) 43 38 35 40 42 49 30 days later Flow rate (gfd) 36.4 52.1 60.3 36.6 34.7 31.3 Salt removal rate (%) 96.8 85.5 66.1 72.7 91.5 93.8 Contact angle (°) 35 25 20 26 39 46 Salt removal rate change rate (%) -2.2 -4.6 -11.5 -16.5 -6.6 -4.8 Contact angle change (°) -8 -13 -15 -14 -3 -3

division Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 First solution Formula 1 (n = 2, wt%) 3 One One One One One Formula 2 (n = 3, wt%) - - - - - - Second amine compound (% by weight) 0.1 0.5 0.5 0.5 0.5 0.5 Phenolic Compounds (wt%) 0.05 0.35 0.35 0.35 0.35 0.35 First and Second Amine Compound Weight Ratio 1: 0.03 1: 0.5 1: 0.5 1: 0.5 1: 0.5 1: 0.5 First Amine and Phenolic Compound Weight Ratio 1: 0.017 1: 0.35 1: 0.35 1: 0.35 1: 0.35 1: 0.35 Second solution H ₂ SO ₄ (% concentration) - - - - - 000.5 NaOH (% concentration) 0.15 0.005 0.015 1.8 2.5 - Early Flow rate (gfd) 14.8 23.1 30.3 37.6 43.2 23.6 Salt removal rate (%) 99.4 98.7 98.5 90.3 87 98.5 Contact angle (°) 62 41 40 36 33 42 30 days later Flow rate (gfd) 18.8 28.8 38.9 42.8 47.7 29.1 Salt removal rate (%) 98.5 94.7 94.2 86 79 91 Contact angle (°) 59 35 35 31 23 37 Salt removal rate change rate (%) -0.9 -4 -4.3 -4.3 -8 -7.5 Contact angle change (°) -3 -6 -5 -5 -10 -5

division Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 First solution Formula 1 (n = 2, wt%) One One One - - - Formula 2 (n = 3, wt%) - - - 0.3 1.5 3 Second amine compound (% by weight) 0.5 0.5 0.5 One 0.5 0.1 Phenolic Compounds (wt%) 0.35 0.35 0.35 0.35 0.35 0.05 First and Second Amine Compound Weight Ratio 1: 0.5 1: 0.5 1: 0.5 1: 3.3 1: 0.33 1: 0.03 First Amine and Phenolic Compound Weight Ratio 1: 0.35 1: 0.35 1: 0.35 1: 1.17 1: 0.23 1: 0.017 Second solution H ₂ SO ₄ (% concentration) 0.015 1.8 2.5 - - - NaOH (% concentration) - - - 0.15 0.15 0.15 Early Flow rate (gfd) 27.3 31.1 41.7 45.5 38.4 35.5 Salt removal rate (%) 98.6 93.5 88.7 93.6 94.1 97.6 Contact angle (°) 40 38 33 43 44 47 30 days later Flow rate (gfd) 42.5 42.1 45.3 121 44.2 66.4 Salt removal rate (%) 91.4 86.4 82.3 10.5 85.3 80.1 Contact angle (°) 34 33 23 8 39 27 Salt removal rate change rate (%) -7.2 -7.1 -6.4 -83.1 -8.8 -17.5 Contact angle change (°) -6 -5 -10 -35 -5 -20

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 First solution Formula 1 (n = 2, wt%) - One One One - Formula 2 (n = 3, wt%) - - - - One Second amine compound (% by weight) 0.5 - 0.5 - - Phenolic Compounds (wt%) 0.35 0.35 - - - First and Second Amine Compound Weight Ratio - - 1: 0.5 - - First Amine and Phenolic Compound Weight Ratio - 1: 0.35 - - - Second solution H ₂ SO ₄ (% concentration) - - - - - NaOH (% concentration) 0.15 0.15 0.15 0.15 0.15 Early Flow rate (gfd) 20.2 36.9 21.1 20.6 24.2 Salt removal rate (%) 87.6 87.9 98.8 96.3 98.9 Contact angle (°) 48 51 54 54 55 30 days later Flow rate (gfd) 199 53 28.6 46.5 36.5 Salt removal rate (%) 6.4 74.3 93.3 83.8 80.5 Contact angle (°) 5 39 37 41 43 Salt removal rate change rate (%) -81.2 -13.6 -5.5 -12.5 -18.4 Contact angle change (°) -43 -12 -17 -13 -12

division Comparative Example 6 Comparative Example 7 Comparative Example 8 First solution Formula 1 (n = 2, wt%) - One One Formula 2 (n = 3, wt%) - - - Second amine compound (% by weight) 0.5 0.5 0.5 Phenolic Compounds (wt%) - 0.35 - First and Second Amine Compound Weight Ratio - 1: 0.5 1: 0.5 First Amine and Phenolic Compound Weight Ratio - 1: 0.35 - Second solution H ₂ SO ₄ (% concentration) - - - NaOH (% concentration) 0.15 - - Early Flow rate (gfd) 31.2 21.3 18.8 Salt removal rate (%) 97.5 99 99.2 Contact angle (°) 43 53 55 30 days later Flow rate (gfd) 205 26.2 24.4 Salt removal rate (%) 3.3 92.2 97.6 Contact angle (°) 7 47 52 Salt removal rate change rate (%) -94.2 -6.8 -1.6 Contact angle change (°) -36 -6 -3

As can be seen from Table 1 to Table 6, the nanomembrane according to the present invention has excellent acid resistance, and even if it is immersed in 15% by weight of sulfuric acid for 30 days or longer, it does not lose its function as a separator, and the rate of change of the salt removal rate is within 10%. It could be confirmed that it is maintained.

In addition, the nano-membrane according to the present invention, compared to the nano-membrane that does not satisfy the conditions and contents according to the present invention, it was confirmed that the initial flow rate, initial salt removal rate, the flow rate and salt removal rate after 30 days of sulfuric acid immersion are all excellent. .

In addition, the nano-separation membrane according to the present invention was confirmed that the lower the initial contact angle, the more the hydrophilization treatment proceeds, the flow rate is improved, the lower the contact angle change rate is inhibited acid hydrolysis is confirmed that the acid resistance is improved. there was.

Claims (16)

Immersing the porous support in a first solution including a first amine compound, a second amine compound, and a phenolic compound including a compound represented by Formula 1 below; Treating the immersed porous support with a second solution including an acid halogen compound to form a polyamide layer on the surface of the porous support; And Hydrophilic treatment of the porous support on which the polyamide layer is formed; [Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₁₀ alkylene group, and n is an integer of 1 to 100. The method of claim 1, In the general formula 1 R ¹ and R ² are each independently a C ₂ ~ straight-chain alkylene group or a C ₂ ~ C ₆ crushing type alkylene of C _6, and n is the integer flow rate of 1 to 10 improved acid resistance nano membrane Manufacturing method. The method of claim 1, The phenolic compound is pyrocatechol, resorcinol, hydroquinone, pyrogallol and phloroglucinol production method of the acid resistance nano-separation membrane with improved flow rate comprising at least one selected from the group consisting of. The method of claim 1, The second amine-based compound is a method for producing an acid resistant nano-separation membrane with improved flow rate comprising at least one selected from the group consisting of metaphenylenediamine and piperazine. The method of claim 1, The first solution is a method for producing an acid resistant nano-membrane with improved flow rate comprising a first amine compound, a second amine compound and a phenol compound in a weight ratio of 1: 0.04 ~ 2: 0.02 ~ 1. The method of claim 1, The first solution has a flow rate of 0.4 to 40 parts by weight of a hydrophilic polymer containing one or more selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol with respect to 100 parts by weight of the first amine compound Method for producing an improved acid resistant nano separator. The method of claim 1, The acid halogen compound is a method for producing an acid resistant nano-separation membrane with improved flow rate comprising at least one selected from isophthaloyl chloride, trimezoyl chloride and terephthaloyl chloride. The method of claim 1, The hydrophilization treatment is a method of producing an acid resistant nano-membrane with improved flow rate is carried out through a hydrophilization solution of 0.01 ~ 2% concentration. The method of claim 8, The hydrophilization solution is a method for producing an acid resistant nano-membrane with improved flow rate comprising at least one selected from the group consisting of potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydroxide, sulfuric acid, sodium sulfate, sodium sulfite and sodium bicarbonate. The method of claim 1, The hydrophilization treatment is a method of producing an acid resistant nano-membrane with improved flow rate is carried out for 10 to 90 ℃ for 0.1 to 5 minutes. The method of claim 1, The porous support includes a nonwoven fabric and a porous polymer layer, The porous polymer layer has an average thickness of 10 to 200㎛, acid-resistant nano with improved flow rate formed of at least one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride Method for producing a separator. Porous support; And A first solution containing a first amine compound, a second amine compound, and a phenolic compound containing a compound represented by the following Formula 1 on the surface of the porous support, and a second solution containing an acid halogen compound It comprises a polyamide layer formed by polymerization; The polyamide layer is an acid resistant nano separation membrane having an improved hydrophilic surface modified flow rate: [Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₁₀ alkylene group, and n is an integer of 1 to 100. The method of claim 12, The polyamide layer has an average thickness of 0.05 ~ 1 ㎛, The porous support includes a nonwoven fabric having an average thickness of 30 to 300 μm and a porous polymer layer having an average thickness of 10 to 200 μm, The porous polymer layer is an acid resistant nano-separation membrane with improved flow rate formed of at least one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride. The method of claim 12, The nano-separation membrane has an improved flow rate of 25 gfd or more at 25 ° C. and 75 psi, and a salt removal rate of 90% or more. The method of claim 12, The nano-separation membrane is an acid-resistant nano-separation membrane having a flow rate of 30 gfd or more, salt removal rate of 85% or more at 25 ℃ and 75 psi when immersed in 15 wt% sulfuric acid aqueous solution for 30 days. Separation module comprising a nano-membrane of any one of claims 12 to 15.